WO2014178333A1 - パターン形成方法、電子デバイスの製造方法及び電子デバイス - Google Patents
パターン形成方法、電子デバイスの製造方法及び電子デバイス Download PDFInfo
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- WO2014178333A1 WO2014178333A1 PCT/JP2014/061628 JP2014061628W WO2014178333A1 WO 2014178333 A1 WO2014178333 A1 WO 2014178333A1 JP 2014061628 W JP2014061628 W JP 2014061628W WO 2014178333 A1 WO2014178333 A1 WO 2014178333A1
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/325—Non-aqueous compositions
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/38—Treatment before imagewise removal, e.g. prebaking
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
- G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/162—Coating on a rotating support, e.g. using a whirler or a spinner
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2041—Exposure; Apparatus therefor in the presence of a fluid, e.g. immersion; using fluid cooling means
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
Definitions
- the present invention relates to a pattern forming method, an electronic device manufacturing method, and an electronic device that are preferably used in a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal or a thermal head, and a photolithographic lithography process.
- the exposure light source has become shorter and the projection lens has a higher numerical aperture (high NA).
- high NA numerical aperture
- an exposure machine using an ArF excimer laser having a wavelength of 193 nm as a light source has been developed.
- immersion liquid a liquid having a high refractive index
- EUV lithography in which exposure is performed with ultraviolet light having a shorter wavelength (13.5 nm) has also been proposed.
- Patent Document 1 discloses decomposition by the action of an acid, A pattern forming method having a step of developing a resist composition containing a resin containing a repeating unit having a group that generates a polar group using an organic solvent developer is described.
- the present invention relates to a pattern forming method using an organic solvent-based developer, which can reduce the occurrence of scum and can form a pattern with excellent line width uniformity (CDU). It is an object of the present invention to provide an electronic device manufacturing method including a pattern forming method and an electronic device.
- the present invention is as follows. [1]-applying a solvent (S) on the substrate; A step of applying an actinic ray-sensitive or radiation-sensitive resin composition on the substrate coated with the solvent (S) to form an actinic ray-sensitive or radiation-sensitive film; A step of exposing the actinic ray-sensitive or radiation-sensitive film; and a step of developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer containing an organic solvent to form a negative pattern.
- a pattern forming method is
- the actinic ray-sensitive or radiation-sensitive resin composition contains a resin whose solubility in a developer containing an organic solvent is reduced by the action of an acid, a compound that generates an acid upon irradiation with actinic rays or radiation, and a solvent.
- the application of the solvent (S) is performed by discharging the solvent (S) onto the substrate, and the application of the actinic ray-sensitive or radiation-sensitive resin composition is discharged onto the substrate.
- the pattern forming method according to any one of [1] to [4], wherein the actinic ray-sensitive or radiation-sensitive resin composition is discharged after the discharge of the solvent (S) is completed. Including rotating the substrate to form a solvent (S) liquid film for a predetermined time until the discharge is started, the rotation speed is 3000 rpm or less, and the discharge of the solvent (S) is completed. Then, the pattern formation method wherein the time until the discharge of the actinic ray-sensitive or radiation-sensitive resin composition is started is 7.0 seconds or less.
- [8] A method for manufacturing an electronic device, comprising the pattern forming method according to any one of [1] to [7].
- [9] An electronic device manufactured by the method for manufacturing an electronic device according to [8].
- a pattern forming method using an organic solvent-based developer that can suppress the occurrence of scum and can form a pattern with excellent line width uniformity (CDU), and an electronic device including the pattern forming method The manufacturing method and electronic device can be provided.
- the description which does not indicate substitution and non-substitution includes not only a substituent but also a substituent.
- the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
- active light refers to, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet (EUV) rays, X rays, soft X rays, electron rays (EB). Etc.
- light means actinic rays or radiation.
- exposure refers to not only exposure with far ultraviolet rays, X-rays, EUV light, etc., typified by mercury lamps and excimer lasers, but also drawing with particle beams such as electron beams and ion beams, unless otherwise specified. Include in exposure.
- the pattern forming method according to the present invention will be described, and then the actinic ray-sensitive or radiation-sensitive resin composition used in this pattern forming method will be described.
- the pattern forming method includes: -Applying a solvent (S) on the substrate; A film-forming step of forming an actinic ray-sensitive or radiation-sensitive film by applying the actinic ray-sensitive or radiation-sensitive resin composition onto the substrate coated with the solvent (S); An exposure step for exposing the actinic ray-sensitive or radiation-sensitive film; and a development for developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer containing an organic solvent to form a negative pattern. Process.
- the pattern forming method according to the present invention includes a step of applying a predetermined solvent (S) to the substrate before applying the actinic ray-sensitive or radiation-sensitive resin composition onto the substrate (hereinafter referred to as “pre-wet step” or the like).
- pre-wet step it is possible to form a pattern in which the occurrence of scum is suppressed and the line width uniformity of the pattern is further improved.
- the scum has a dissolution delay in the organic solvent-based developer at the bottom of the unexposed portion of the actinic ray-sensitive or radiation-sensitive film, which becomes a residue. Arise. Since the pattern forming method of the present invention includes a pre-wet process, the actinic ray-sensitive or radiation-sensitive film is formed with the solvent remaining on the substrate. It is presumed that the solubility of the organic solvent developer in the unexposed area is improved and the scum is improved.
- solvent (S) the solvent used in the pre-wet process
- solvent (S) the solvent used in the development process and the rinsing process, which will be described later, It is clearly distinguished from the solvent that can be contained in the radiation-sensitive resin composition.
- the pattern forming method of the present invention may include a heating step, and may further include a heating step a plurality of times.
- the pattern formation method of this invention may include the exposure process in multiple times.
- the pattern forming method of the present invention may include a developing step a plurality of times, and in that case, the step of developing using an organic developer and the step of developing using an alkaline developer may be combined.
- the pattern formation method of this invention may further include the rinse process wash
- each step will be described.
- the solvent (S) that can be used in the pre-wet process is not particularly limited as long as it is a solvent in which an actinic ray-sensitive or radiation-sensitive resin composition (hereinafter also referred to as “the composition of the present invention”) described later dissolves. Can be used without any problem.
- the solvent (S) preferably has a vapor pressure at room temperature (20 ° C.) of 0.7 kPa or less, more preferably 0.4 kPa or less, and 0.3 kPa or less. More preferably.
- the vapor pressure of the solvent (S) is a predetermined value or less
- the composition of the present invention is applied on the substrate in the next step, the actinic ray-sensitive or radiation-sensitive film is not exposed. This is preferable because a sufficient amount of the solvent (S) can be left to improve the solubility in the organic solvent developer.
- solvent (S) examples include methyl 3-methoxypropionate (MMP), methyl amyl ketone (MAK), ethyl lactate (EL), propylene glycol monomethyl ether acetate (PGMEA), cyclohexanone, normal pentyl acetate, ethylene glycol, acetic acid Isopentyl, butyl acetate, propylene glycol monomethyl ether (PGME), 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, methylcyclohexanone, phenyl Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetyl acetone, acetonyl acetone, ionone, diacetyl alcohol, acetyl carbinol, acetophenone
- a solvent (S) may be used individually by 1 type, and 2 or more types may be mixed and used for it.
- the method for applying the solvent (S) onto the substrate is not particularly limited.
- the substrate may be adsorbed and fixed to a spinner chuck, and after the solvent (S) is discharged onto the substrate at the center of the wafer, the substrate is rotated by the spinner to form a solvent (S) liquid film.
- the solvent (S) may be applied while rotating the substrate to form a solvent (S) liquid film.
- the liquid film formed may be discontinuous.
- the composition of the present invention which is the next step, is applied on the substrate with the solvent (S) remaining on the substrate to form an actinic ray-sensitive or radiation-sensitive film. It is important that
- the time from the end of the discharge of the solvent (S) to the start of the discharge of the composition of the present invention is preferably 7.0 seconds or less, and 4.0 seconds. Or less, more preferably 2.0 seconds or less.
- the rotation speed is preferably 3000 rpm or less, more preferably 1500 rpm or less, and still more preferably 500 rpm or less.
- the substrate may be rotated from the start of the discharge of the solvent (S), or may be continuously rotated after the discharge of the composition of the present invention is started. Good.
- the substrate to which the solvent (S) is applied is not particularly limited, and an inorganic substrate such as silicon, SiN, SiO 2 or TiN, a coated inorganic substrate such as SOG, a semiconductor manufacturing process such as an IC, A substrate generally used in a manufacturing process of a circuit board such as a liquid crystal or a thermal head, and also in other photofabrication lithography processes can be used.
- the substrate surface may be treated with hexamethyldisilazane (HMDS) before applying the solvent (S) to the substrate.
- HMDS hexamethyldisilazane
- S solvent
- the substrate can be hydrophobized to improve the solvent applicability. From this viewpoint, it is preferable to perform the HMDS treatment.
- an antireflection film formed on the substrate may be used as the substrate to which the solvent (S) is applied.
- the antireflection film a known organic or inorganic antireflection film can be appropriately used.
- the step of exposing the light-sensitive or radiation-sensitive film and the step of developing the actinic light-sensitive or radiation-sensitive film with a developer containing an organic solvent can be performed by a generally known method. .
- the actinic ray-sensitive or radiation-sensitive resin composition is applied to the substrate coated with the solvent (S), for example, in the same manner as the application of the solvent (S) described above, at the center of the wafer.
- the substrate After applying the radiation-sensitive resin composition onto the substrate, the substrate may be rotated with a spinner to form an actinic ray-sensitive or radiation-sensitive film, or the actinic ray-sensitive or radiation-sensitive film while rotating. May be applied to form an actinic ray-sensitive or radiation-sensitive film.
- the rotation speed of the substrate is usually 4000 rpm or less.
- the substrate is rotated at 900 rpm or less for a predetermined time, and then at 1000 rpm or more for a predetermined time. It is preferable to rotate.
- the pattern forming method of the present invention preferably includes a preheating (PB) process after the film forming process and before the exposure process.
- the pattern forming method of the present invention preferably includes a post-exposure heating (PEB) step after the exposure step and before the development step.
- PB preheating
- PEB post-exposure heating
- the heating temperature is preferably 70 to 130 ° C., more preferably 80 to 120 ° C. for both PB and PEB.
- the heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds. Heating can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like. The reaction of the exposed part is promoted by baking, and the sensitivity and pattern profile are improved.
- ⁇ Exposure process> Although there is no restriction
- KrF excimer laser 248 nm
- ArF excimer laser (193 nm)
- F 2 excimer laser 157 nm
- X-ray EUV
- EUV 13 nm
- electron beam etc.
- KrF excimer laser, ArF excimer laser, EUV or electron beam are preferable, and ArF excimer laser is more preferable.
- an immersion exposure method can be applied in the exposure process of the present invention.
- the immersion exposure method can be combined with a super-resolution technique such as a phase shift method or a modified illumination method.
- the immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a refractive index temperature coefficient as small as possible so as to minimize distortion of the optical image projected onto the film.
- an ArF excimer laser (wavelength: 193 nm)
- an additive liquid that decreases the surface tension of water and increases the surface activity may be added in a small proportion.
- This additive is preferably one that does not dissolve the resist layer on the wafer and can ignore the influence on the optical coating on the lower surface of the lens element.
- an aliphatic alcohol having a refractive index substantially equal to that of water is preferable, and specific examples include methyl alcohol, ethyl alcohol, isopropyl alcohol and the like.
- distilled water is preferable as the water to be used because it causes distortion of the optical image projected on the resist when an opaque material or impurities whose refractive index is significantly different from that of water are mixed with 193 nm light. Further, pure water filtered through an ion exchange filter or the like may be used.
- the electrical resistance of the water used as the immersion liquid is preferably 18.3 MQcm or more, the TOC (organic substance concentration) is preferably 20 ppb or less, and deaeration treatment is preferably performed.
- an additive that increases the refractive index may be added to water, or heavy water (D 2 O) may be used instead of water.
- the receding contact angle of the resist film formed by using the actinic ray-sensitive or radiation-sensitive resin composition in the present invention is 70 ° or more at a temperature of 23 ⁇ 3 ° C. and a humidity of 45 ⁇ 5%, and through the immersion medium. Suitable for exposure, preferably 75 ° or more, more preferably 75 to 85 °. If the receding contact angle is too small, it cannot be suitably used for exposure through an immersion medium, and the effect of reducing water residue (watermark) defects cannot be sufficiently exhibited. In order to achieve a preferable receding contact angle, it is preferable to include the hydrophobic resin (HR) in the actinic ray-sensitive or radiation-sensitive composition. Alternatively, the receding contact angle may be improved by forming a coating layer (so-called “topcoat”) of a hydrophobic resin composition on the resist film.
- topcoat a coating layer
- the immersion head In the immersion exposure process, the immersion head needs to move on the wafer following the movement of the exposure head to scan the wafer at high speed to form the exposure pattern.
- the contact angle of the immersion liquid with respect to the resist film is important, and the resist is required to follow the high-speed scanning of the exposure head without remaining droplets.
- a step of washing the surface of the film may be included at least one after the film forming step and before the exposure step, and after the exposure step and before the post-exposure heating (PEB) step. Good. Thereby, it is possible to suppress the occurrence of defects (hereinafter also referred to as “water remaining defects”) due to the immersion liquid (immersion water) remaining on the resist surface by immersion exposure.
- This cleaning step is performed, for example, by using pure water to discharge pure water rinse while rotating the wafer on which the actinic ray-sensitive or radiation-sensitive film is formed at a predetermined speed. May be formed.
- a step of removing pure water by inert gas blowing and / or spin drying may be included.
- the development step in the pattern forming method of the present invention is performed using a developer (organic developer) containing an organic solvent. As a result, a negative pattern is formed.
- organic developer polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents can be used.
- ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Examples include cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetylalcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.
- ester solvent examples include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, Examples include ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, and propyl lactate. .
- the alcohol solvents include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, alcohols such as n-octyl alcohol and n-decanol, glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, Diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethylbuta Glycol ether solvents such as Lumpur can be mentioned.
- Examples of the ether solvent include dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.
- Examples of amide solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like.
- Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.
- the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents and ester solvents, and in particular, butyl acetate or ketone as the ester solvent.
- a developer containing methyl amyl ketone (2-heptanone) as a system solvent is preferred.
- a plurality of solvents may be mixed, or may be used by mixing with a solvent other than those described above or water.
- the water content of the developer as a whole is preferably less than 10% by mass, and more preferably substantially free of moisture. That is, the amount of the organic solvent used in the organic developer is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less, with respect to the total amount of the developer.
- the vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C.
- the surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used.
- fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, US Pat. No. 5,405,720,
- it is a nonionic surfactant.
- it does not specifically limit as a nonionic surfactant, It is still more preferable to use a fluorochemical surfactant or a silicon-type surfactant.
- the amount of the surfactant used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total amount of the developer.
- a developing method for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc.
- dip method a method in which a substrate is immersed in a tank filled with a developer for a certain period of time
- paddle a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time
- spray method a method of spraying the developer on the substrate surface
- the discharge pressure of the discharged developer (the flow rate per unit area of the discharged developer) is As an example, it is preferably 2 mL / sec / mm 2 or less, more preferably 1.5 mL / sec / mm 2 or less, and still more preferably 1 mL / sec / mm 2 or less.
- the flow rate is no particular lower limit on the flow rate, but 0.2 mL / sec / mm 2 or more is preferable in consideration of throughput. Details of this are described in Japanese Patent Application Laid-Open No. 2010-232550, especially paragraphs 0022 to 0029.
- a step of stopping development may be performed while substituting with another solvent.
- the pattern forming method of the present invention includes a plurality of development steps, a step of developing using an alkaline developer and a step of developing using an organic developer may be combined. As a result, FIG. 1-FIG. 11 and the like, it can be expected that a pattern having a half of the spatial frequency of the optical image can be obtained.
- the alkali developer that can be used is not particularly limited, but generally, it is 2.38% by mass of tetramethylammonium hydroxide.
- An aqueous solution is desirable.
- an appropriate amount of alcohol or surfactant may be added to the alkaline aqueous solution.
- the alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
- the pH of the alkali developer is usually from 10.0 to 15.0.
- pure water can be used, and an appropriate amount of a surfactant can be added.
- ⁇ Rinse process> After the step of developing using an organic developer, it is preferable to include a rinse step of washing using a rinse solution.
- the rinsing liquid is not particularly limited as long as the resist pattern is not dissolved, and a solution containing a general organic solvent can be used.
- a rinsing liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents is used. It is preferable.
- hydrocarbon solvent ketone solvent, ester solvent, alcohol solvent, amide solvent and ether solvent
- hydrocarbon solvent ketone solvent, ester solvent, alcohol solvent, amide solvent and ether solvent
- the step of washing with a rinse liquid containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, and amide solvents is performed, and the step of washing with a rinsing solution containing a monohydric alcohol is particularly preferred.
- a cleaning step is performed using a rinse liquid containing a monohydric alcohol having 5 or more carbon atoms.
- examples of the monohydric alcohol used in the rinsing step include linear, branched, and cyclic monohydric alcohols. Specific examples include 1-hexanol, 2-hexanol, and 4-methyl-2-pen. Tanol, 1-pentanol, 3-methyl-1-butanol and the like can be used. A plurality of these components may be mixed, or may be used by mixing with an organic solvent other than the above.
- the water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.
- the vapor pressure of the rinsing solution used after the step of developing with a developer containing an organic solvent is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less at 20 ° C. 12 kPa or more and 3 kPa or less are the most preferable.
- the cleaning method is not particularly limited. For example, a method of continuing to discharge the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid onto the substrate surface (spray method), etc. can be applied. Among these, a cleaning process is performed by a spin coating method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm.
- the developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed by baking.
- the heating step after the rinsing step is usually performed at 40 to 160 ° C., preferably 70 to 95 ° C., usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.
- the organic developer, alkali developer, and / or rinse solution used in the present invention preferably have few impurities such as various fine particles and metal elements.
- these chemicals are manufactured in a clean room, and filtered with various filters such as Teflon (registered trademark) filters, polyolefin filters, ion exchange filters, etc. It is preferable to reduce impurities.
- the metal element the metal element concentrations of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn are all preferably 10 ppm or less, and preferably 5 ppm or less. More preferred.
- the storage container for the developer and the rinsing liquid is not particularly limited, and containers such as polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin that are used for electronic materials can be used as appropriate.
- containers such as polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin that are used for electronic materials can be used as appropriate.
- a container having a small amount of components eluted from the inner wall of the container into the chemical solution As such a container, a container whose inner wall is a perfluoro resin (for example, FluoroPure PFA composite drum (wetted inner surface; PFA resin lining) manufactured by Entegris), steel drum can (wetted inner surface; zinc phosphate coating) manufactured by JFE ).
- the pattern obtained by the pattern forming method of the present invention is generally suitably used as an etching mask for a semiconductor device, but can also be used for other purposes.
- Other uses include, for example, guide pattern formation in DSA (Directed Self-Assembly) (see, for example, ACS Nano Vol. 4, No. 8, Page 4815-4823), use as a core material (core) of a so-called spacer process (for example, JP-A-3-270227, JP-A-2013-164509, etc.).
- the present invention also relates to an electronic device manufacturing method including the pattern forming method of the present invention described above, and an electronic device manufactured by this manufacturing method.
- the electronic device of the present invention is suitably mounted on electrical and electronic equipment (home appliances, OA / media related equipment, optical equipment, communication equipment, etc.).
- the actinic ray-sensitive or radiation-sensitive resin composition (hereinafter also referred to as “the composition of the present invention”) used in the pattern forming method according to the present invention is a development containing one or more organic solvents by the action of an acid.
- the resin contains a resin whose solubility in the liquid decreases, a compound that generates an acid upon irradiation with actinic rays or radiation, and a solvent as essential components.
- Resin whose solubility in a developer containing an organic solvent is reduced by the action of an acid As a resin whose solubility in a developer containing an organic solvent is reduced by the action of an acid, for example, the main chain or side chain of the resin, or Resins (hereinafter referred to as “acid-decomposable resin” or “resin (A ) ”).
- the acid-decomposable group preferably has a structure protected by a group capable of decomposing and leaving a polar group by the action of an acid.
- Preferred polar groups include carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), and sulfonic acid groups.
- a preferred group as the acid-decomposable group is a group in which the hydrogen atom of these groups is substituted with a group capable of leaving with an acid.
- Examples of the group leaving with an acid include —C (R 36 ) (R 37 ) (R 38 ), —C (R 36 ) (R 37 ) (OR 39 ), —C (R 01 ) (R 02 ). ) (OR 39 ) and the like.
- R 36 to R 39 each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
- R 36 and R 37 may be bonded to each other to form a ring.
- R 01 and R 02 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
- the acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. More preferably, it is a tertiary alkyl ester group.
- the resin (A) preferably has a repeating unit having an acid-decomposable group.
- the repeating unit include the following.
- Rx represents a hydrogen atom, CH 3 , CF 3 , or CH 2 OH.
- Rxa and Rxb each represents an alkyl group having 1 to 4 carbon atoms.
- Xa 1 represents a hydrogen atom, CH 3 , CF 3 , or CH 2 OH.
- Z represents a substituent, and when a plurality of Zs are present, the plurality of Zs may be the same as or different from each other.
- p represents 0 or a positive integer.
- Specific examples and preferred examples of Z are the same as specific examples and preferred examples of the substituent that each group such as Rx 1 to Rx 3 may have.
- Xa represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom.
- Xa 1 represents a hydrogen atom, CH 3 , CF 3 , or CH 2 OH.
- One type of repeating unit having an acid-decomposable group may be used, or two or more types may be used in combination. Although the combination in the case of using 2 types together is not specifically limited, For example, the following combinations are mentioned preferably.
- the content of the repeating unit having an acid-decomposable group contained in the resin (A) (when there are a plurality of repeating units having an acid-decomposable group, the total) is based on the total repeating units of the resin (A), It is preferably 15 mol% or more, more preferably 20 mol% or more, further preferably 25 mol% or more, and particularly preferably 40 mol% or more.
- Resin (A) may contain a repeating unit having a lactone structure or a sultone structure.
- repeating unit having a group having a lactone structure or a sultone structure are shown below, but the present invention is not limited thereto.
- the content of the repeating unit having a lactone structure or a sultone structure is 5 to 60 mol% with respect to all the repeating units in the resin (A). It is preferably 5 to 55 mol%, more preferably 10 to 50 mol%.
- the resin (A) may have a repeating unit having a cyclic carbonate structure. Although a specific example is given how, this invention is not limited to these.
- R A 1 represents a hydrogen atom or an alkyl group (preferably a methyl group).
- Resin (A) may have a repeating unit having a hydroxyl group or a cyano group.
- repeating unit having a hydroxyl group or a cyano group are given below, but the present invention is not limited thereto.
- Resin (A) may have a repeating unit having an acid group.
- the resin (A) may or may not contain a repeating unit having an acid group, but when it is contained, the content of the repeating unit having an acid group is relative to all the repeating units in the resin (A). It is preferably 25 mol% or less, and more preferably 20 mol% or less. When resin (A) contains the repeating unit which has an acid group, content of the repeating unit which has an acid group in resin (A) is 1 mol% or more normally.
- repeating unit having an acid group Specific examples of the repeating unit having an acid group are shown below, but the present invention is not limited thereto.
- Rx represents H, CH 3 , CH 2 OH, or CF 3 .
- the resin (A) further has an alicyclic hydrocarbon structure and / or an aromatic ring structure that does not have a polar group (for example, the acid group, hydroxyl group, cyano group), and has a repeating unit that does not exhibit acid decomposability. be able to.
- the content is preferably 3 to 30 mol%, more preferably 5 to 25 mol%, based on all repeating units in the resin (A).
- Ra represents H, CH 3 , CH 2 OH, or CF 3 .
- the resin (A) used in the composition of the present invention has substantially no aromatic ring from the viewpoint of transparency to ArF light (specifically,
- the ratio of the repeating unit having an aromatic group in the resin is preferably 5 mol% or less, more preferably 3 mol% or less, ideally 0 mol%, that is, no aromatic group).
- the resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.
- the form of the resin (A) in the present invention may be any of random type, block type, comb type, and star type.
- Resin (A) is compoundable by the radical, cation, or anion polymerization of the unsaturated monomer corresponding to each structure, for example. It is also possible to obtain the desired resin by conducting a polymer reaction after polymerization using an unsaturated monomer corresponding to the precursor of each structure.
- the resin (A) used in the composition of the present invention has substantially no aromatic ring from the viewpoint of transparency to ArF light (specifically,
- the ratio of the repeating unit having an aromatic group in the resin is preferably 5 mol% or less, more preferably 3 mol% or less, ideally 0 mol%, that is, no aromatic group).
- the resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.
- the composition of the present invention contains a resin (D) described later, it is preferable that the resin (A) does not contain a fluorine atom and a silicon atom from the viewpoint of compatibility with the resin (D).
- the resin (A) used in the composition of the present invention is preferably such that all of the repeating units are composed of (meth) acrylate-based repeating units.
- all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are methacrylate repeating units and acrylate repeating units.
- the acrylate-based repeating unit is preferably 50 mol% or less of the total repeating units.
- the resin (A) When the composition of the present invention is irradiated with KrF excimer laser light, electron beam, X-ray, high energy light beam (EUV, etc.) having a wavelength of 50 nm or less, the resin (A) has a repeating unit having an aromatic ring. May be.
- the repeating unit having an aromatic ring is not particularly limited, and is also exemplified in the above description of each repeating unit, but a styrene unit, a hydroxystyrene unit, a phenyl (meth) acrylate unit, a hydroxyphenyl (meth) acrylate. Examples include units.
- the resin (A) is a resin having a hydroxystyrene-based repeating unit and a hydroxystyrene-based repeating unit protected by an acid-decomposable group, a repeating unit having the aromatic ring, and (meth) Examples thereof include a resin having a repeating unit in which the carboxylic acid moiety of acrylic acid is protected by an acid-decomposable group.
- the resin (A) in the present invention can be synthesized and purified according to a conventional method (for example, radical polymerization).
- a conventional method for example, radical polymerization.
- the weight average molecular weight of the resin (A) in the present invention is 7,000 or more, preferably 7,000 to 200,000, more preferably 7,000 as described above in terms of polystyrene by GPC method. 50,000 to 50,000, still more preferably 7,000 to 40,000,000, particularly preferably 7,000 to 30,000. When the weight average molecular weight is less than 7000, the solubility in an organic developer becomes too high, and there is a concern that a precise pattern cannot be formed.
- the degree of dispersion is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and particularly preferably 1.4 to 2.0. Those in the range are used.
- the smaller the molecular weight distribution the better the resolution and the resist shape, the smoother the sidewall of the resist pattern, and the better the roughness.
- the blending ratio of the resin (A) in the entire composition is preferably 30 to 99% by mass, more preferably 60 to 95% by mass in the total solid content.
- the resin (A) may be used alone or in combination.
- composition ratio of a repeating unit is a molar ratio
- this invention is not limited to these.
- supported by resin (A) is also illustrated.
- the resin exemplified below is an example of a resin that can be suitably used particularly during EUV exposure or electron beam exposure.
- composition in the present invention is usually a compound that generates acid upon irradiation with actinic ray or radiation (hereinafter referred to as “compound (B)” or “acid generator”. ").
- compound (B) that generates an acid upon irradiation with actinic rays or radiation is preferably a compound that generates an organic acid upon irradiation with actinic rays or radiation.
- photo-initiator of photocation polymerization photo-initiator of photo-radical polymerization, photo-decoloring agent of dyes, photo-discoloring agent, irradiation of actinic ray or radiation used for micro resist, etc.
- the known compounds that generate an acid and mixtures thereof can be appropriately selected and used.
- Examples include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.
- the acid generator can be synthesized by a known method. For example, [0200] to [0210] of JP2007-161707A, JP2010-100595A, and WO2011 / 093280 [ [0051] to [0058], [0382] to [0385] of International Publication No. 2008/153110, Japanese Patent Application Laid-Open No. 2007-161707, and the like.
- the acid generator can be used alone or in combination of two or more.
- the content of the compound that generates an acid upon irradiation with actinic rays or radiation in the composition is preferably 0.1 to 30% by mass, more preferably 0.5%, based on the total solid content of the composition of the present invention. -25% by mass, more preferably 3-20% by mass, particularly preferably 3-15% by mass.
- Solvents that can be used in preparing the composition of the present invention include, for example, alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, alkyl lactate esters, alkyl alkoxypropionates, cyclic lactones (preferably carbon And organic solvents such as monoketone compounds (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate.
- solvents that can be used in preparing the composition of the present invention include, for example, alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, alkyl lactate esters, alkyl alkoxypropionates, cyclic lactones (preferably carbon And organic solvents such as monoketone compounds (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate.
- a mixed solvent obtained by mixing a solvent containing a hydroxyl group in the structure and a solvent not containing a hydroxyl group may be used as the organic solvent.
- the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group can be selected as appropriate.
- the solvent containing a hydroxyl group alkylene glycol monoalkyl ether, alkyl lactate and the like are preferable, and propylene glycol monomethyl ether ( PGME, also known as 1-methoxy-2-propanol), ethyl lactate is more preferred.
- alkylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, monoketone compound which may contain a ring, cyclic lactone, alkyl acetate and the like are preferable, and among these, propylene glycol monomethyl ether Acetate (PGMEA, also known as 1-methoxy-2-acetoxypropane), ethyl ethoxypropionate, 2-heptanone, ⁇ -butyrolactone, cyclohexanone, butyl acetate are particularly preferred, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2 -Heptanone is most preferred.
- PGMEA propylene glycol monomethyl ether Acetate
- ethyl ethoxypropionate 2-heptanone
- ⁇ -butyrolactone cyclohexanone
- the mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. .
- a mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is particularly preferred from the viewpoint of coating uniformity.
- Solvents may be used alone or in combination of two or more.
- the solvent preferably contains propylene glycol monomethyl ether acetate, and is preferably a propylene glycol monomethyl ether acetate single solvent or a mixed solvent of two or more containing propylene glycol monomethyl ether acetate.
- Hydrophobic resin (D) The composition of the present invention may contain a hydrophobic resin (hereinafter also referred to as “hydrophobic resin (D)” or simply “resin (D)”), particularly when applied to immersion exposure.
- the hydrophobic resin (D) is preferably different from the resin (A).
- the hydrophobic resin (D) is unevenly distributed in the film surface layer, and when the immersion medium is water, the static / dynamic contact angle of the resist film surface with water is improved, and the immersion liquid followability is improved. be able to. Further, EUV exposure is preferable because it can be expected to suppress so-called outgassing.
- the hydrophobic resin (D) is preferably designed to be unevenly distributed at the interface as described above. However, unlike the surfactant, the hydrophobic resin (D) does not necessarily need to have a hydrophilic group in the molecule. There is no need to contribute to uniform mixing.
- the hydrophobic resin (D) is selected from any one of “fluorine atom”, “silicon atom”, and “CH 3 partial structure contained in the side chain portion of the resin” from the viewpoint of uneven distribution in the film surface layer. It is preferable to have the above, and it is more preferable to have two or more.
- the weight average molecular weight in terms of standard polystyrene of the hydrophobic resin (D) is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, still more preferably 2,000 to 15,000. is there.
- hydrophobic resin (D) may be used alone or in combination.
- the content of the hydrophobic resin (D) in the composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, based on the total solid content in the composition of the present invention. More preferably, it is 1 to 7% by mass.
- the molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 5, more preferably 1 to 3, and still more preferably from the viewpoints of resolution, resist shape, resist pattern sidewall, roughness, and the like. It is in the range of 1-2.
- the hydrophobic resin (D) various commercially available products can be used, and the hydrophobic resin (D) can be synthesized according to a conventional method (for example, radical polymerization).
- a conventional method for example, radical polymerization
- a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours.
- the dropping polymerization method is added, and the dropping polymerization method is preferable.
- the reaction solvent, the polymerization initiator, the reaction conditions (temperature, concentration, etc.) and the purification method after the reaction are the same as those described for the resin (A), but in the synthesis of the hydrophobic resin (D),
- the concentration of the reaction is preferably 30 to 50% by mass.
- hydrophobic resin (D) Specific examples of the hydrophobic resin (D) are shown below.
- the following table shows the molar ratio of repeating units in each resin (corresponding to each repeating unit in order from the left), the weight average molecular weight, and the degree of dispersion.
- Basic compound The composition of the present invention preferably contains a basic compound.
- a basic compound may be used individually by 1 type, and may be used in combination of 2 or more type.
- composition of the present invention is also referred to as a basic compound or an ammonium salt compound (hereinafter referred to as “compound (N)”) whose basicity is reduced by irradiation with actinic rays or radiation. ) Is preferably contained.
- the compound (N) is preferably a compound (N-1) having a basic functional group or an ammonium group and a group that generates an acidic functional group upon irradiation with actinic rays or radiation. That is, the compound (N) is a basic compound having a basic functional group and a group capable of generating an acidic functional group upon irradiation with actinic light or radiation, or an acidic functional group upon irradiation with an ammonium group and active light or radiation. An ammonium salt compound having a group to be generated is preferable.
- Examples of the compound (N) include the following.
- examples of the compound (N) include the compounds (A-1) to (A-44) described in US Patent Application Publication No. 2010/0233629, and US patent applications.
- the compounds (A-1) to (A-23) described in JP 2012/0156617 A can also be preferably used in the present invention.
- the molecular weight of the compound (N) is preferably 500 to 1,000.
- composition of the present invention may or may not contain the compound (N), but when it is contained, the content of the compound (N) is from 0.1 to 0.1 on the basis of the solid content of the composition. It is preferably 20% by mass, more preferably 0.1 to 10% by mass.
- composition of the present invention is different from the compound (N) as a basic compound in order to reduce the change in performance over time from exposure to heating. ) May be contained.
- Preferred examples of the basic compound (N ′) include compounds having structures represented by the following formulas (A ′) to (E ′).
- RA 200 , RA 201 and RA 202 may be the same or different and are a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20), a cycloalkyl group (preferably having a carbon number of 3 to 20) or an aryl group (having a carbon number of 6-20), where RA 201 and RA 202 may combine with each other to form a ring.
- RA 203 , RA 204 , RA 205 and RA 206 may be the same or different and each represents an alkyl group (preferably having 1 to 20 carbon atoms).
- the alkyl group may have a substituent.
- the alkyl group having a substituent include an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, and a carbon group having 1 to 20 carbon atoms.
- a cyanoalkyl group is preferred.
- alkyl groups in general formulas (A ′) and (E ′) are more preferably unsubstituted.
- the basic compound (N ′) include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, and more preferable specific examples include an imidazole structure. , Diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, trialkylamine structure, aniline structure or pyridine structure compound, alkylamine derivative having hydroxyl group and / or ether bond, aniline derivative having hydroxyl group and / or ether bond Etc.
- Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole and the like.
- Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene, 1,8-diazabicyclo [5,4, 0] Undecaker 7-ene and the like.
- Examples of the compound having an onium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically, triphenylsulfonium hydroxide, tris (t-butylphenyl) Examples include sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide, and the like.
- the compound having an onium carboxylate structure is a compound having an onium hydroxide structure in which the anion moiety is converted to a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate.
- Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine.
- Examples of the compound having an aniline structure include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline and the like.
- alkylamine derivative having a hydroxyl group and / or an ether bond examples include ethanolamine, diethanolamine, triethanolamine, and tris (methoxyethoxyethyl) amine.
- aniline derivatives having a hydroxyl group and / or an ether bond examples include N, N-bis (hydroxyethyl) aniline.
- Preferred examples of the basic compound further include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group.
- Specific examples thereof include, but are not limited to, compounds (C1-1) to (C3-3) exemplified in [0066] of US Patent Application Publication No. 2007/0224539. Absent.
- composition of the present invention may contain a nitrogen-containing organic compound having a group capable of leaving by the action of an acid as one kind of basic compound.
- a nitrogen-containing organic compound having a group capable of leaving by the action of an acid as one kind of basic compound.
- this compound for example, specific examples of the compound are shown below.
- the above compound can be synthesized, for example, according to the method described in JP-A-2009-199021.
- the molecular weight of the basic compound (N ′) is preferably 250 to 2000, more preferably 400 to 1000. From the viewpoint of further reduction in LWR and uniformity of local pattern dimensions, the molecular weight of the basic compound is preferably 400 or more, more preferably 500 or more, and even more preferably 600 or more. .
- These basic compounds (N ′) may be used in combination with the compound (N), or may be used alone or in combination of two or more.
- the chemically amplified resist composition in the present invention may or may not contain the basic compound (N ′), but when it is contained, the amount of the basic compound (N ′) used depends on the chemically amplified resist composition. Based on the solid content of the product, it is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass.
- the composition of the present invention may contain an onium salt represented by the following general formula (6A) or (6B) as a basic compound.
- This onium salt is expected to control the diffusion of the generated acid in the resist system in relation to the acid strength of the photoacid generator usually used in the resist composition.
- Ra represents an organic group. However, those in which a fluorine atom is substituted for a carbon atom directly bonded to a carboxylic acid group in the formula are excluded.
- X + represents an onium cation.
- Rb represents an organic group. However, those in which a fluorine atom is substituted for a carbon atom directly bonded to the sulfonic acid group in the formula are excluded.
- X + represents an onium cation.
- the atom directly bonded to the carboxylic acid group or sulfonic acid group in the formula is preferably a carbon atom.
- the fluorine atom does not substitute for the carbon atom directly bonded to the sulfonic acid group or carboxylic acid group.
- Examples of the organic group represented by Ra and Rb include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms. Alternatively, a heterocyclic group having 3 to 30 carbon atoms can be used. In these groups, some or all of the hydrogen atoms may be substituted.
- alkyl group, cycloalkyl group, aryl group, aralkyl group and heterocyclic group may have include a hydroxyl group, a halogen atom, an alkoxy group, a lactone group, and an alkylcarbonyl group.
- Examples of the onium cation represented by X + in the general formulas (6A) and (6B) include a sulfonium cation, an ammonium cation, an iodonium cation, a phosphonium cation, and a diazonium cation. Among these, a sulfonium cation is more preferable.
- an arylsulfonium cation having at least one aryl group is preferable, and a triarylsulfonium cation is more preferable.
- the aryl group may have a substituent, and the aryl group is preferably a phenyl group.
- the structure demonstrated in the compound (B) can also be mentioned preferably.
- a specific structure of the onium salt represented by the general formula (6A) or (6B) is shown below.
- the composition of the present invention is a compound included in the formula (I) of JP2012-189977A, or a compound of formula (I) of JP2013-6827A as a basic compound.
- Onium in one molecule such as a compound represented by formula (I) in JP2013-8020A, a compound represented by formula (I) in JP2012-252124A, and the like
- a compound having both a salt structure and an acid anion structure (hereinafter also referred to as a betaine compound) may be contained.
- the onium salt structure include a sulfonium, iodonium, and ammonium structure, and a sulfonium or iodonium salt structure is preferable.
- the acid anion structure is preferably a sulfonate anion or a carboxylic acid anion. Examples of this compound include the following.
- composition of the present invention may further contain a surfactant.
- a surfactant fluorine and / or silicon surfactant (fluorine surfactant, silicon surfactant, surfactant having both fluorine and silicon atoms) It is more preferable to contain either one or two or more.
- composition of the present invention contains a surfactant
- an exposure light source of 250 nm or less, particularly 220 nm or less it is possible to provide a resist pattern with less adhesion and development defects with good sensitivity and resolution. Become.
- fluorine-based and / or silicon-based surfactant examples include surfactants described in [0276] of US Patent Application Publication No. 2008/0248425.
- surfactants are derived from fluoroaliphatic compounds produced by the telomerization method (also referred to as the telomer method) or the oligomerization method (also referred to as the oligomer method).
- a surfactant using a polymer having a fluoroaliphatic group can be used.
- the fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.
- Megafac F178, F-470, F-473, F-475, F-476, F-472 manufactured by DIC Corporation
- surfactants other than fluorine-based and / or silicon-based surfactants described in [0280] of US Patent Application Publication No. 2008/0248425 can also be used. These surfactants may be used alone or in several combinations.
- the amount of the surfactant used is preferably 0.0001 to 2% by mass, more preferably 0, based on the total amount of the composition (excluding the solvent). 0005 to 1% by mass.
- the amount of the surfactant added is 10 ppm or less with respect to the total amount of the actinic ray-sensitive or radiation-sensitive resin composition (excluding the solvent), the surface unevenness of the hydrophobic resin is increased. As a result, the surface of the resist film can be made more hydrophobic, and the water followability during immersion exposure can be improved.
- composition of the present invention may contain a carboxylic acid onium salt.
- carboxylic acid onium salts include those described in US Patent Application Publication No. 2008/0187860 [0605] to [0606].
- the content is generally 0.1 to 20% by mass, preferably 0.5 to 10% by mass, based on the total solid content of the composition. %, More preferably 1 to 7% by mass.
- composition of this invention may also contain what is called an acid growth agent as needed.
- the acid proliferating agent is particularly preferably used when performing the pattern forming method of the present invention by EUV exposure or electron beam irradiation. Although it does not specifically limit as a specific example of an acid multiplication agent, For example, the following is mentioned.
- a dye In the composition of the present invention, a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, a dissolution inhibitor, and a compound that promotes solubility in a developer (for example, a molecular weight of 1000 or less) A phenol compound, an alicyclic compound having a carboxyl group, or an aliphatic compound).
- composition of the present invention is preferably used in a film thickness of 30 to 250 nm, more preferably in a film thickness of 30 to 200 nm, from the viewpoint of improving resolution.
- the solid content concentration of the composition of the present invention is usually 1.0 to 10% by mass, preferably 2.0 to 5.7% by mass, and more preferably 2.0 to 5.3% by mass. By setting the solid content concentration within the above range, the resist solution can be uniformly applied on the substrate.
- the solid content concentration is the weight percentage of the weight of other resist components excluding the solvent with respect to the total weight of the chemically amplified resist composition.
- the composition of the present invention is used by dissolving the above-described components in a predetermined organic solvent, preferably the mixed solvent, filtering the solution, and applying the solution on a predetermined support (substrate).
- the pore size of the filter used for filter filtration is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, and still more preferably 0.03 ⁇ m or less made of polytetrafluoroethylene, polyethylene, or nylon.
- filter filtration for example, as in JP-A-2002-62667, circulation filtration may be performed, or filtration may be performed by connecting a plurality of types of filters in series or in parallel.
- the composition may be filtered multiple times. Furthermore, you may perform a deaeration process etc. with respect to a composition before and behind filter filtration.
- ⁇ Resist preparation 1> The components shown in the table below are dissolved in the solvent shown in the table in a solid content of 3.5% by mass, and each is filtered through a polyethylene filter having a pore size of 0.03 ⁇ m, and the actinic ray-sensitive or radiation-sensitive resin composition. (Resist composition) was prepared.
- hydrophobic resin As the hydrophobic resin, the following 1b to 4b were used.
- W-1 MegaFuck F176 (Dainippon Ink Chemical Co., Ltd .; Fluorine)
- W-2 Megafuck R08 (Dainippon Ink & Chemicals, Inc .; fluorine and silicon)
- W-3 Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd .; silicon-based)
- W-4 Troisol S-366 (manufactured by Troy Chemical Co., Ltd.)
- W-5 KH-20 (Asahi Glass Co., Ltd.)
- W-6 PolyFox PF-6320 (manufactured by OMNOVA Solutions Inc .; fluorine system) ⁇ Solvent>
- solvents SG-1 to SG-5 shown below were used.
- SL-1 Propylene glycol monomethyl ether acetate (PGMEA)
- SL-2 Ethyl lactate
- SL-3 Propylene glycol monomethyl ether (PGME)
- SL-4 Cyclohexanone
- SL-5 ⁇ -Butyrolactone ⁇ Pattern formation> A 300 mm diameter (12 inch diameter) silicon wafer was treated with hexamethyldisilazane (HMDS) and baked at 115 ° C. for 60 seconds.
- HMDS hexamethyldisilazane
- an antireflection film was formed, or an antireflection film was formed after forming an SOC film (Table 6).
- the antireflection film ARC29SR (95 nm / manufactured by Nissan Chemical Co., Ltd.), the silicon-containing antireflection film HM825 (manufactured by 30 nm / Brewer Science), and the SOC film 110D (manufactured by 100% Brewer Science) were each applied on the substrate. Baking was performed at 205 ° C. for 60 seconds to form a film.
- A: When there is no scum and the substrate surface is clean. B: When scum is slightly seen and a slight resist film residue is scattered on the substrate. C: Scum is clearly confirmed, and the resist film residue is present on the substrate. When D: There are many scum and thick resist film residue is scattered on the substrate E: When scum can check the connection between residues at the bottom between patterns ⁇ CDU (Line width uniformity) evaluation Using S9380 (manufactured by Hitachi, Ltd.), the line width was measured for a total of 55 shots within the wafer surface (Threshold 50), and the line width uniformity within the wafer surface was measured. The evaluation results are shown as standard deviation (nm, 3 ⁇ ) from the average value obtained. A smaller value indicates better performance.
- ⁇ Resist preparation 2> The components shown in Table 7 below were dissolved in the solvent shown in the same table so that the solid content was 1.6% by mass, and each was filtered through a polyethylene filter having a pore size of 0.05 ⁇ m.
- Example 34 (Formation of resist film)
- the chemical amplification resist composition Ar-33 was subjected to pattern formation evaluation including ejection of the solvent (S) according to Example 1 except that the exposure source was changed to EUV (extreme ultraviolet) light. Good pattern formation could be performed.
- EUV extreme ultraviolet
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Abstract
Description
[1]-基板上に溶剤(S)を塗布する工程、
-感活性光線性又は感放射線性樹脂組成物を、溶剤(S)が塗布された前記基板上に塗布して感活性光線性又は感放射線性膜を形成する工程、
-前記感活性光線性又は感放射線性膜を露光する工程、及び
-露光した前記感活性光線性又は感放射線性膜を、有機溶剤を含む現像液で現像してネガ型パターンを形成する工程
を含むパターン形成方法。
[7] 前記露光は193nm以下の波長で行われる、[1]~[8]のいずれか1項に記載のパターン形成方法。
[9] [8]に記載の電子デバイスの製造方法により製造された電子デバイス。
本明細書に於ける基(原子団)の表記に於いて、置換及び無置換を記していない表記は置換基を有さないものと共に置換基を有するものをも包含するものである。例えば「アルキル基」とは、置換基を有さないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含するものである。
本発明に係るパターン形成方法は、
-基板上に溶剤(S)を塗布する工程、
-感活性光線性又は感放射線性樹脂組成物を、溶剤(S)が塗布された前記基板上に塗布して感活性光線性又は感放射線性膜を形成する製膜工程、
-前記感活性光線性又は感放射線性膜を露光する露光工程、及び
-露光した前記感活性光線性又は感放射線性膜を、有機溶剤を含む現像液で現像してネガ型パターンを形成する現像工程を含む。
また、本発明のパターン形成方法は、現像工程を複数回含んでいてもよく、その場合において有機系現像液を用いて現像する工程とアルカリ現像液を用いて現像する工程とを組み合わせてもよい。
また、本発明のパターン形成方法は、現像工程の後にリンス液を用いて洗浄するリンス工程を更に含んでもよい。
以下、各工程について説明する。
プリウェット工程において用い得る溶剤(S)としては、後述する感活性光線性又は感放射線性樹脂組成物(以下、「本発明の組成物」などともいう)が溶解する溶剤であれば特に限定されることなく用いることができる。本発明の一形態において、溶剤(S)は、室温(20℃)での蒸気圧が0.7kPa以下であることが好ましく、0.4kPa以下であることがより好ましく、0.3kPa以下であることが更に好ましい。このように溶剤(S)の蒸気圧が所定値以下であると、次の工程において本発明の組成物が基板上に塗布される際に、感活性光線性又は感放射線性膜の未露光部における有機溶剤系現像液に対する溶解度を向上させるのに十分な量の溶剤(S)が残存し得ることなるため好ましい。
溶剤(S)が塗布された基板に対する感活性光線性又は感放射線性樹脂組成物の塗布は、例えば、上述した溶剤(S)の塗布と同様に、ウェハー中心の位置で感活性光線性又は感放射線性樹脂組成物を基板上に塗布した後、スピンナーにて基板を回転させて感活性光線性又は感放射線性膜を形成してもよいし、回転させながら感活性光線性又は感放射線性膜を塗布して感活性光線性又は感放射線性膜を形成してもよい。
本発明のパターン形成方法は、一形態において、製膜工程の後かつ露光工程の前に、前加熱(PB;Prebake)工程を含むことも好ましい。
また、本発明のパターン形成方法は、他の形態において、露光工程の後かつ現像工程の前に、露光後加熱(PEB;Post Exposure Bake)工程を含むことも好ましい。
加熱時間は30~300秒が好ましく、30~180秒がより好ましく、30~90秒が更に好ましい。
加熱は通常の露光・現像機に備わっている手段で行うことができ、ホットプレート等を用いて行ってもよい。
ベークにより露光部の反応が促進され、感度やパターンプロファイルが改善する。
本発明の露光方法に用いられる光源波長に制限は無いが、赤外光、可視光、紫外光、遠紫外光、極紫外光、X線、電子線等を挙げることができ、好ましくは250nm以下、より好ましくは220nm以下、特に好ましくは1~200nmの波長の遠紫外光、具体的には、KrFエキシマレーザー(248nm)、ArFエキシマレーザー(193nm)、F2エキシマレーザー(157nm)、X線、EUV(13nm)、電子線等であり、KrFエキシマレーザー、ArFエキシマレーザー、EUV又は電子線が好ましく、ArFエキシマレーザーであることがより好ましい。
このような添加剤としては、例えば、水とほぼ等しい屈折率を有する脂肪族系のアルコールが好ましく、具体的にはメチルアルコール、エチルアルコール、イソプロピルアルコール等が挙げられる。水とほぼ等しい屈折率を有するアルコールを添加することにより、水中のアルコール成分が蒸発して含有濃度が変化しても、液体全体としての屈折率変化を極めて小さくできるといった利点が得られる。
前記後退接触角が小さすぎると、液浸媒体を介して露光する場合に好適に用いることができず、かつ水残り(ウォーターマーク)欠陥低減の効果を十分に発揮することができない。好ましい後退接触角を実現する為には、前記の疎水性樹脂(HR)を前記感活性光線性または放射線性組成物に含ませることが好ましい。あるいは、レジスト膜の上に、疎水性の樹脂組成物によるコーティング層(いわゆる「トップコート」)を形成することにより後退接触角を向上させてもよい。
本発明のパターン形成方法における現像工程は、有機溶剤を含有する現像液(有機系現像液)を用いて行われる。これによりネガ型のパターンが形成される。
アミド系溶剤としては、例えば、N-メチル-2-ピロリドン、N,N-ジメチルアセトアミド、N,N-ジメチルホルムアミド、ヘキサメチルホスホリックトリアミド、1,3-ジメチル-2-イミダゾリジノン等が使用できる。
炭化水素系溶剤としては、例えば、トルエン、キシレン等の芳香族炭化水素系溶剤、ペンタン、ヘキサン、オクタン、デカン等の脂肪族炭化水素系溶剤が挙げられる。
すなわち、有機系現像液に対する有機溶剤の使用量は、現像液の全量に対して、90質量%以上100質量%以下であることが好ましく、95質量%以上100質量%以下であることが好ましい。
界面活性剤としては特に限定されないが、例えば、イオン性や非イオン性のフッ素系及び/又はシリコン系界面活性剤等を用いることができる。これらのフッ素及び/又はシリコン系界面活性剤として、例えば特開昭62-36663号公報、特開昭61-226746号公報、特開昭61-226745号公報、特開昭62-170950号公報、特開昭63-34540号公報、特開平7-230165号公報、特開平8-62834号公報、特開平9-54432号公報、特開平9-5988号公報、米国特許第5405720号明細書、同5360692号明細書、同5529881号明細書、同5296330号明細書、同5436098号明細書、同5576143号明細書、同5294511号明細書、同5824451号明細書記載の界面活性剤を挙げることができ、好ましくは、非イオン性の界面活性剤である。非イオン性の界面活性剤としては特に限定されないが、フッ素系界面活性剤又はシリコン系界面活性剤を用いることが更に好ましい。
アルカリ現像液のアルカリ濃度は、通常0.1~20質量%である。
アルカリ現像液のpHは、通常10.0~15.0である。
アルカリ現像の後に行うリンス処理におけるリンス液としては、純水を使用し、界面活性剤を適当量添加して使用することもできる。
<リンス工程>
有機系現像液を用いて現像する工程の後には、リンス液を用いて洗浄するリンス工程を含むことが好ましい。このリンス液としては、レジストパターンを溶解しなければ特に制限はなく、一般的な有機溶剤を含む溶液を使用することができる。前記リンス液としては、炭化水素系溶剤、ケトン系溶剤、エステル系溶剤、アルコール系溶剤、アミド系溶剤及びエーテル系溶剤からなる群より選択される少なくとも1種類の有機溶剤を含有するリンス液を用いることが好ましい。
前記各成分は、複数混合してもよいし、上記以外の有機溶剤と混合し使用してもよい。
リンス工程においては、有機溶剤を含む現像液を用いる現像を行ったウェハを前記の有機溶剤を含むリンス液を用いて洗浄処理する。洗浄処理の方法は特に限定されないが、たとえば、一定速度で回転している基板上にリンス液を吐出しつづける方法(回転塗布法)、リンス液が満たされた槽中に基板を一定時間浸漬する方法(ディップ法)、基板表面にリンス液を噴霧する方法(スプレー法)、などを適用することができ、この中でも回転塗布方法で洗浄処理を行い、洗浄後に基板を2000rpm~4000rpmの回転数で回転させ、リンス液を基板上から除去することが好ましい。また、リンス工程の後に加熱工程(Post Bake)を含むことも好ましい。ベークによりパターン間及びパターン内部に残留した現像液及びリンス液が除去される。リンス工程の後の加熱工程は、通常40~160℃、好ましくは70~95℃で、通常10秒~3分、好ましくは30秒から90秒間行う。
本発明の電子デバイスは、電気電子機器(家電、OA・メディア関連機器、光学用機器及び通信機器等)に、好適に、搭載されるものである。
本発明に係るパターン形成方法において使用される感活性光線性又は感放射線性樹脂組成物(以下、「本発明の組成物」ともいう)は、酸の作用により1種類以上の有機溶剤を含む現像液に対する溶解度が減少する樹脂、活性光線又は放射線の照射により酸を発生する化合物、及び、溶剤を必須成分として含有する。
酸の作用により有機溶剤を含む現像液に対する溶解度が減少する樹脂としては、例えば、樹脂の主鎖又は側鎖、あるいは、主鎖及び側鎖の両方に、酸の作用により分解し、極性基を生じる基(以下、「酸分解性基」ともいう)を有する樹脂(以下、「酸分解性樹脂」又は「樹脂(A)」ともいう)を挙げることができる。
この繰り返し単位としては、以下が挙げられる。
具体例中、Rxは、水素原子、CH3、CF3、又はCH2OHを表す。Rxa、Rxbはそれぞれ炭素数1~4のアルキル基を表す。Xa1は、水素原子、CH3、CF3、又はCH2OHを表す。Zは、置換基を表し、複数存在する場合、複数のZは互いに同じであっても異なっていてもよい。pは0又は正の整数を表す。Zの具体例及び好ましい例は、Rx1~Rx3などの各基が有し得る置換基の具体例及び好ましい例と同様である。
本発明における組成物は、通常、活性光線又は放射線の照射により酸を発生する化合物(以下、「化合物(B)」又は「酸発生剤」ともいう)を含有する。活性光線又は放射線の照射により酸を発生する化合物(B)としては、活性光線又は放射線の照射により有機酸を発生する化合物であることが好ましい。
態様(B´)として、以下のような繰り返し単位が挙げられるが、これに限定されるものではない。
本発明の組成物は、通常、溶剤を含有する。
本発明の組成物を調製する際に使用することができる溶剤としては、例えば、アルキレングリコールモノアルキルエーテルカルボキシレート、アルキレングリコールモノアルキルエーテル、乳酸アルキルエステル、アルコキシプロピオン酸アルキル、環状ラクトン(好ましくは炭素数4~10)、環を有しても良いモノケトン化合物(好ましくは炭素数4~10)、アルキレンカーボネート、アルコキシ酢酸アルキル、ピルビン酸アルキル等の有機溶剤を挙げることができる。
本発明の組成物は、特に液浸露光に適用する際、疎水性樹脂(以下、「疎水性樹脂(D)」又は単に「樹脂(D)」ともいう)を含有してもよい。なお、疎水性樹脂(D)は、前記樹脂(A)とは異なることが好ましい。
疎水性樹脂(D)の組成物中の含有量は、本発明の組成物中の全固形分に対し、0.01~10質量%が好ましく、0.05~8質量%がより好ましく、0.1~7質量%が更に好ましい。
本発明の組成物は、塩基性化合物を含有することが好ましい。塩基性化合物は、1種単独で使用してもよいし、2種以上を組み合わせて使用してもよい。
化合物(N)の分子量は、500~1000であることが好ましい。
RA200、RA201及びRA202は、同一でも異なってもよく、水素原子、アルキル基(好ましくは炭素数1~20)、シクロアルキル基(好ましくは炭素数3~20)又はアリール基(炭素数6~20)を表し、ここで、RA201とRA202は、互いに結合して環を形成してもよい。RA203、RA204、RA205及びRA206は、同一でも異なってもよく、アルキル基(好ましくは炭素数1~20)を表す。
また、塩基性化合物(N’)としては、アミンオキシド構造を有する化合物も用いることもできる。この化合物の具体例としては、トリエチルアミンピリジン N-オキシド、トリブチルアミン N-オキシド、トリエタノールアミン N-オキシド、トリス(メトキシエチル)アミン N-オキシド、トリス(2-(メトキシメトキシ)エチル)アミン=オキシド、2,2’,2”-ニトリロトリエチルプロピオネート N-オキシド、N-2-(2-メトキシエトキシ)メトキシエチルモルホリン N-オキシド、その他特開2008-102383に例示されたアミンオキシド化合物が使用可能である。
Raは、有機基を表す。但し、式中のカルボン酸基に直接結合する炭素原子にフッ素原子が置換しているものを除く。
X+は、オニウムカチオンを表す。
Rbは、有機基を表す。但し、式中のスルホン酸基に直接結合する炭素原子にフッ素原子が置換しているものを除く。
X+はオニウムカチオンを表す。
本発明の組成物は、更に界面活性剤を含有してもよい。本発明の組成物が界面活性剤を含有する場合、フッ素及び/又はシリコン系界面活性剤(フッ素系界面活性剤、シリコン系界面活性剤、フッ素原子とケイ素原子の両方を有する界面活性剤)のいずれか、あるいは2種以上を含有することがより好ましい。
これらの界面活性剤は単独で使用してもよいし、また、いくつかの組み合わせで使用してもよい。
本発明の組成物は、カルボン酸オニウム塩を含有してもよい。このようなカルボン酸オニウム塩は、米国特許出願公開2008/0187860号明細書[0605]~[0606]に記載のものを挙げることができる。
下表に示す成分を同表に示す溶剤に固形分で3.5質量%溶解させ、それぞれを0.03μmのポアサイズを有するポリエチレンフィルターでろ過して、感活性光線性又は感放射線性樹脂組成物(レジスト組成物)を調製した。
樹脂(A)として、下記に示すPol-01~1~Pol-21を使用した。なお、これら樹脂は公知のラジカル重合法により合成し、精製した。また、これら樹脂について、GPC(溶媒:THF)測定により、重量平均分子量(Mw:ポリスチレン換算)、数平均分子量(Mn:ポリスチレン換算)及び分散度(Mw/Mn、以下「Pd」)を算出した。また、1H-NMR測定により、組成比(モル比)を算出した。
界面活性剤としては、以下に示すW-1~W-6を用いた。
W-2: メガファックR08(大日本インキ化学工業(株)製;フッ素及びシリコン系)
W-3: ポリシロキサンポリマーKP-341(信越化学工業(株)製;シリコン系)
W-4: トロイゾルS-366(トロイケミカル(株)製)
W-5: KH-20(旭硝子(株)製)
W-6: PolyFox PF-6320(OMNOVA Solutions Inc.製;フッ素系)
<溶剤>
溶剤としては、以下に示すSG-1~SG-5を使用した。
SL-2:乳酸エチル
SL-3:プロピレングリコールモノメチルエーテル(PGME)
SL-4:シクロヘキサノン
SL-5:γ-ブチロラクトン
<パターン形成>
300mm口径(12インチ口径)シリコンウェハをヘキサメチルジシラザン(HMDS)処理し、115℃で60秒間ベークを行った。
・スカム評価
上記で得られた感度において、レジストパターン間の底部を走査型電子顕微鏡(日立社製S-4800)により観察し、下記の5段階評価を行った。
B:スカムが若干見られ、基板上に僅かなレジスト膜残りが散見される場合
C:スカムが明らかに確認でき、基板上にレジストの膜残りが見られる場合
D:スカムが多く、基板上に厚みのあるレジスト膜残りが散見される場合
E:スカムにより、パターン間の底部に残渣による繋がり確認できる場合
・CDU(線幅均一性)評価
上記で得られた繰り返しパターンをS9380((株)日立製作所製)により、ウェハ面内の計55ショットについて線幅を測定し(Threshhold=50)、ウェハ面内の線幅均一性を測定した。評価結果は得られた平均値からの標準偏差(nm、3σ)で示した。値が小さいほど良好な性能であることを示す。
下記表7に示す成分を同表に示す溶剤に固形分で1.6質量%となるように溶解させ、それぞれを0.05μmのポアサイズを有するポリエチレンフィルターでろ過して、表7に示す感活性光線性又は感放射線性樹脂組成物(化学増幅型レジスト組成物)Ar-33及びAr-34を調製した。
(レジスト膜の形成)
化学増幅型レジスト組成物Ar-33を、露光源をEUV(極紫外)光に変えた以外は、上記実施例1に準じて、溶剤(S)の吐出を含むパターン形成評価を行ったところ、良好なパターン形成を行うことができた。
上記と同様にして、表7の化学増幅型レジスト組成物Ar-34に於いてもレジストパターン形成を行うことができた。
Claims (9)
- -基板上に溶剤(S)を塗布する工程、
-感活性光線性又は感放射線性樹脂組成物を、溶剤(S)が塗布された前記基板上に塗布して感活性光線性又は感放射線性膜を形成する工程、
-前記感活性光線性又は感放射線性膜を露光する工程、及び
-露光した前記感活性光線性又は感放射線性膜を、有機溶剤を含む現像液で現像してネガ型パターンを形成する工程
を含むパターン形成方法。 - 前記感活性光線性又は感放射線性樹脂組成物が、酸の作用により有機溶剤を含む現像液に対する溶解度が減少する樹脂、活性光線又は放射線の照射により酸を発生する化合物及び溶剤を含有する、請求項1に記載のパターン形成方法。
- 溶剤(S)の20℃における蒸気圧が0.7kPa以下である、請求項1に記載のパターン形成方法。
- 基板上に塗布された前記溶剤(S)が残存している状態で前記感活性光線性又は感放射線性膜が形成される、請求項1に記載のパターン形成方法。
- 前記溶剤(S)の塗布が溶剤(S)を基板上に吐出することにより行われ、前記感活性光線性又は感放射線性樹脂組成物の塗布が該組成物を基板上に吐出することにより行われる請求項1に記載のパターン形成方法であって、溶剤(S)の吐出が終了してから前記感活性光線性又は感放射線性樹脂組成物の吐出が開始されるまでの間の所定時間に基板を回転させて溶剤(S)の液膜を形成することを含み、その回転速度が3000rpm以下であり、且つ、溶剤(S)の吐出が終了してから前記感活性光線性又は感放射線性樹脂組成物の吐出が開始されるまでの時間が7.0秒以下であるパターン形成方法。
- 前記露光は液浸液を介して行われる、請求項1に記載のパターン形成方法。
- 前記露光は193nm以下の波長で行われる、請求項1に記載のパターン形成方法。
- 請求項1に記載のパターン形成方法を含む、電子デバイスの製造方法。
- 請求項8に記載の電子デバイスの製造方法により製造された電子デバイス。
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